Process for dyeing



Patented Sept. so, 1930 JAMES nannrnnr, aunannnnrenmm,nnn rnaov ononnnr, or BmcxL Y, mn-

, cnnsrna, ENGLAND, assmnons 'ro BRITISH nyns'rurrs coaronarzon LIMITED,

or BLAGKLEY, marronnsrnn, ENGLAND- 3 rimmin Application aieasua 4, 19 28 Serial'Ko.j282,8 82, and is area as... June 7, 1927.

,. According to our co pending application,

'- Serial N o. 271,399.newfdisazodyestufis are nitrobenzidine with I. one molecule of {an amino-naphtholsulphonicacid or an N-sub- 'stituted derivative thereof and one'molecu'le of any of the usual coupling components. Many of the dyestuffsthus obtained possess Y the. valuable property of dyeing a regenerated 1o cellulose such as viscose silk, in even shades.

In further development of this discovery, we have now found that many] of the disazo dyes obtained by combining the tetrazo compounds of other 2 :2-subst1tuted derivatives of 4 4-diaminodiphenyl .with two molecules of the same or different coupling components I also possess the valuable property'of giving even dyeings on regenerated cellulose silks.

The present application is a continuation in part of our above recited copending application Serial No. 271,399. '1 1 The'present invention relates to the dyeing .in even, level shades of regenerated cellulose materials, for example,"viscose silks, by ap- 2 plying to the said regenerated cellulose materials the disazo dyestuffs obtained by combining the tetrazo derivative of a- 2:2'-sub-,

stituted 4::4J-diaminodiphenyl with two molecules of the same or different coupling components. The said disazo dyestuffs may be represented by the following general formula p 1 r e v i where Rrepresents the residue of the coupling component and R "represents a substituent atom or group, and when sulphonic groups are present, there must not be more than tWo such groups contained in the disazo dyestuffs. For the production of satisfactory results, we havefound that there must not be present in the dyestuff molecule more than two sulphonic acid groups, which groups may occupy the 2:2-positions in the diphenyl nucleus or may be contained in one or in both of the coupling components applied. The

choice of coupling components is accordingly determined by the nature of the 2:2-subcember, 1910, cation in, the dyeing of wool, particularly the nucleus. Some of -.the ;dyestufis' ofthe aforementioned type are obtained by combining-Q-nitro'and 2:2-di-," I

'jspecificationsNd 10,331of the 27th April,

alreadyc-lmown-(see, for instance, British 1910, Bloxain and No. 28,67 8 of the 9th Del3loxa'm) and have found applifor the production on Wool of dyeings which are fast to milling. They possess, however, only, a poor affinity for cotton and have therefore no value for dyeing the cotton fibre. It was not to be foreseen that these dyestuffs would have a good afiinity for regenerated cellulose silk, such as viscose silk, and in particular that they would possess the valuable property of dyeing viscose silk, in even shades.

It is well knownthat the artificial silks made from regenerated cellulose give great diflicultyin dyeing, owing to the fact that the' fabric generally possesses an uneven 'afiinity for the usual types ofsubstantive cotton colours, in'consequence ofwhich the dyeings obtained-are unlevel. Our invention is therefore of great value in the art of dyehing silks of this type.

The following examples illustrate the in vention, but we do not limit ourselves to the conditions-described therein. The parts are by weight.

. Example] The goods to be dyed (100 parts) are entered cold into 5,000 parts of water containing 3 parts of soap and 1 part of the dyestuif obtained by tetrazotizing 253 parts of 2 :2 dichloro 4:14; diaminodiphenyl and combining with 138 parts of salicylic acid and 239 parts of 2-amino-8-naphthol-6-sulphonic acid in alkaline solution. The dye bath is brought to the boil and maintained at or near that temperature for hour, about 15 parts of Glaubers salt being added before the finish. .The silk is then removed from the bath, rinsed and dried. It is dyed a very even orange-brown shade.

Example 2 v formed by combining one molecule of 2: 2'-diinethylbenzidine (in-tolidine) with one molecule of salicylic acid and. one molecule of 2-amino-8-naphtliol-6-siilphonic acid in alkalinc solution the viscose silk is dyed an even maroon shade.

The following table illustrates the shades we obtain but the invention is not limited to the examples contained therein; the couplings with pyrazolone derivatives are performed in acid solution; all other couplings mentioned in the table are carried out in the wherein R represents a coupling component and R represents a substituent atom or group, the said disazo dye containing two or presence of alkali.

, less sulphonic groups.

2:2-benzidine derivative tetrazotized do 2:2'-dimethyl benzldine (m-tolidine) do do Benzidino-2:2-dicarboxyllc acid do do Benzidine-2:2-disulphonic acid 2:2-dinitrobenzidine Combined with 1 (2) shad" g Salicylic id 2-phelpylamino-8-niiphtl1ol-6-sulph0nic Yellowish-br own aci Beta-oxynaphtlioic acid 2-ainino-8-naplitliol-6-sulphonic acid Claret 2-amino-8-nepl1thol-6-sulphonic acid 2-ainino-8-napl1tliol-6sulphouic acid Maroon do Resorcinol Orange-hrown 1 (2z5 dichloro 4-sulphophenyl)-3- 2-amino-5-naphthol-7-sulphonic acid Orange-red inethyl-5-pyrazolone 1-(4l-sulphop enyl-)-3-methyl-5-pyra=-i 2-iimino-8-napl1tho1-6-sulphonic acid Light-brown 20 one Salicylic acid l-phenylaniino 8 naphthalene siil Yellowish-red phonic acid d l-emino-8-naphtliol-4-sulphonic acid Claret do 2-emino-8-napl1th0l-6-sulphonic acid Red (coupled in acid solution) do z-phenyleminol-naphthol-fi-sulphonlc Brown g I acid (coupled in alkaline solution) z-amino-S-nephthol-G-sulplionic acid 2-21mlD0'8-llHDl'liZhOlJi-SlllDllODlC acid Reddish-brown Beta-naplithol 1-arag1o-8-naphthol-2:4-disulplionic Reddish-violet aci Salicylic acid 2-112hen%amino-8-naplitliol-6-sulplion- Brown 0 aci 1-phenyl-S-methyl-S-pyrazolone l-phen l-3-methyl-5- azolone Yellow 2-phenyamino-5-naphth01-7-sulphon- Resorcihol pyr Crimson ic aci 1-(4'isulphopheny1)-3-metliy1-5-p yr a- Beta-naphthol Orange 20 one 1-pl1enyl-3-niethyl-5-pyrazolone l-phenyl-3-methyl-5-pyrazolone Yellow Salicylic acid 2-arnino-8-naphthol-6-sulphonic acid Yellowish-brown A generic formula which can be used to represent the dyes of Examples 1 and 2 15 as follows:

wherein R represents the coupled residue of salicylic acid, R represents the coupled residue of 2-amino-8-naphthol-6-sulphonic acid and R represents Cl or CH \Vhat we claim and desire to secure by Letters Patent is 1. The process for dyeing regenerated cellulose materials in level shades which consists in applying to the said regenerated cellulose materials a disazo dye obtained by coupling tetrazotized 2:2-substituted 4:4- diaminodiphenyls with one molecular. proportion of one component and one molecular proportion of a different component, the said (lisazo dye containing not more than two sulphonic groups.

2. The regenerated cellulose materials dyed with disazo dyes, the said dyes comprising the coupled residues of 2:2 substituted 4 4 diaminodiphenyls and of molecular proportions of coupling components, and containing not more than two sulphonic groups.

4; The process for dyeing regenerated cellulose materials in even level shades, which comprises applying to the said regenerated cellulose materials a disazo dye having the following general formula Ri R1 where R represents a coupling component and R represents N 0 alkyl, Cl, SO H, or COOH groups, the said disazo dye containing two or less sulphonic groups.

5. The process for dyeing regenerated cellulose materials in even level shades, which comprises applying to the said regenerated cellulose materials a disazo dye having the following general formula where R represents a coupling component and R represents a substituent atom or group, the said regenerated dyed cellulose materials having even level shades.

8. The. regenerated cellulose materials dyed with a disazo dye having the following general formula where R represents a coupling component and R represents N0 alkyl, Cl, 80 1i, or COOH groups, the said regenerated dyed cellulose materials having even level shades.

9. The regenerated cellulose materials dyed with a disazo dye having the following general formula Where R represents a coupling component, at

least one coupling component being an aminonaphthol sulphonic acid and R represents N0 alkyl, Cl, SO H, or COOH groups. the said regenerated dyed cellulose materials having even level shades.

10. The process of dyeing regenerated cellulose materials in level shades which comprises applying to the said regenerated cellulose materials a disazo dye obtained by coupling tetrazotized 2:2-substituted 4:4-diaminodiphenyls with molecular proportions of coupling components, the said disazo dye containing not more than two sulphonic groups.

11. In the dyeing of regenerated cellulose materials, the process. which comprises applying to the said regenerated materials a disazo dye having the following general formula R1 R1 l wherein It represents the coupled residue of salicylic acid, R represents the coupled residue of 2-amino-8-naphthol-(3-sulphonic acid and R represents C1 or CH 12. In the dyeing of regenerated cellulose materials, the process which comprises applying to the said regenerated materials a disazodye having the following general formula wherein R represents the coupled residue of salicylic acid, R represents the coupled residue of 2-amino-8-naphthol-6sulphonic acid and R represents a chlorine atom.

13. The regenerated cellulose materials dyed with a disazo dye having the following general formula wherein R represents the coupled residue of salicylic acid, R represents the coupled residue of 2-amino-8-naphthol-6-sulphonic acid and R represents Cl or CH the said regenerated dyed cellulose materials having even level shades.

14. The regenerated cellulose materials dyed -\vith a disazo dye having the following general formula wherein R represents the coupled residue of salicylic acid, R represents the coupled resi due of 2-amino-8-naphthol-6-sulphonic acid and R represents a chlorine atom, the said regenerated dyed cellulose materials having even level shades.

In testimony whereof we afiix our signatures.

JAMES BADD ILEY. PERCY CHORLEY. RAINALD BRIGHTMAN. 

